Phosphor containing gallium



United States Patent cc 2,727,866

. Patented Dec. 20, 1955 a red cathodoluminescent emission, and a spectral distribution that is about the same as for copper activated 2,727,866 zinc selenide; however, there is an increase in emission intensity of about 75% over copper activated zinc sele- PHOSPHOR CONTAINING GALLIUM nide. The product has a very strong fluorescence with a Simon Larach, New Brunswick, N. 1., assiguor to Radio fast power'law'type decay Corporation of America, a corporation of D l The table shows the ettect of various additives on the peak wavelength and relative peak emission intensity of N0 Drawing' ,APPlicafion May 1953 some zinc selenide phosphors under cathode ray excitasenal 358,189 tion. The relative peak emission intensity is relative to 10 i 1, 252 3 1 rhombohedral manganese activated zinc silicate considered to be 100. All metallic additions were 0.01% by weight as the nitrate. Chloride additions were 2.0%

by weight as ammonium chloride. Chloride additions This iHVEZZtlOD relates t0 luminescent materials and, made in the presence of alu ninum or gallium additigns more particularly, to improved red-emitting cathodowere d b h th d f th i ti luminescent phosphors containing gallium, and to meth- Ods of Preparation of the improved phosphors. Table.-Eflect of various additives on zinc selenide Red-emitting cathodoluminescent phosphors are findphosphors ing great utility as the red phosphor component in kinescopes for color television. One of the most eifective Activator Additives Peak Wavegroups of red emitters are the ZIIlC and zinc-cadmlum length, A. Intensity selenides containing a copper activator and a halide additive. However, the best reported peak emission intensity 6,370 0.31 of this type phosphor is only about 40 as compared to an 6 020 (1) 2 0 emission intensity of 100 for rhombohedral manganese activated zinc silicate. '238 8'; It has been demonstrated that gallium may be substi- 6:470 tuted for part or preferably all of the halide additive. @333 {f8 Such a substitution does not materially increase the peak Cu Ga 61470 3710 emission intensity, but instead decreases the fluorescence Ga and 6470 m0 and increases the phosphorescence of the phosphor to produce a phosphor with a long decay period. It is also Emlssmn too weak to measure Well known that it is difficult to incorporate both a halide The materials used to P p the phosphors of this and gallium into a phosphor by ordinary method G 1. invention should be the purest materials obtainable, since lium in the presence of a halide forms materials which Small amcuhts ofiimpurifies affect the emission of the volatilize during the crystallization of the phosphor. Phosphor- The Zmc Selenide may be Prepared by the It is an object of this invention to provide red-emitting method disclosed by Thomseh in Patent cathodoluminescent phosphors having a high peak emis- 2,534,562 issusd December 1952- sion intensity While copper and gallium were introduced as nitrates Another Qhiect f this invention is to Provide copper. in the example, these cations may be introduced in activated Zinc d Zineeadmium seienide phosphors other forms, for example as carbonates and sulphates. having halide and gallium additives incorporateri Copper additions may range from 0.002 to 0.05 the it is a f h object f this invention to Provide an preferred addition being 0.01%. Gallium additions may improved method for preparing a red-emitting cathodorange from 0.005 to 0.05%; the preferred addition being luminescent phosphor having a high peak emission in- The hahde y he a ChlOIlde, bromlde OI ten it iodide and may be introduced as ammonium salts or as In general, th present invention comprises the i the salt of an alkali metal or an alkaline earth metal. corporation of activator quantities of copper, gallium Halide additihhs y range from to 7 the and a halide, selected from the group consisting of chlo- K Pheferred addltlon helhg cadmlum y be rid bromides d i did i a phosphor consisting stituted for part or all of the ZlIlC 1n the above-described essentially of a selenide of at least one metal selected from exampie- Increasing Substitutions 0f Cadmium f Z nC th class consisting f i d d i The method shifts the emission characteristics of the product toward of the present invention comprises firing, to about 900 the longer Wavelength end of h spficlfllmt The furnace C. for about 30 minutes, at least one selenide selected athlosphfife Should e neutral, that It h u n t react fr m th class consisting f i d d i i h with any of the constituents. Nltrogen, helium and argon activator quantities of gallium and copper; and then reare recommended ahhospheresfiring the resultant product to about 900 C. for about There has thus been described a Series Of m- 30 minutes with a small quantity of a halogen containing Pf l'ediehh'ttihg h pp Zinc-Cadmium l cgmpound, mdes containing galllum and a halide; and a new and EXAMPLE, improved method for preparing these phosphors.

What is claimed is: 1. A method of preparing a phosphor material which comprises mixing activator quantities of gallium and copper salts with a selenide of at least one metal selected from the class consisting of zinc and cadmium, firing Mix 100 grams of pure zinc selenide with 0.01 gram of copper as the nitrate and 0.01 gram of gallium as the nitrate. To facilitate mixing, the constituents may be slurried with Water. The mixture is dried to about {raj-Shifted to a silica firing "F and fired at said mixture at about 900 C. for about 30 minutes in about 900 C. ror about 30 minutes in an atmosphere a neutral atmosphere, mixing i fi d Product with of nitfogehwhen the pf cooled, 1t 15 {nixed activator quantities of a halide selected from the group h 2 grams of ammonium chloride n h mlxture consisting of iodides, bromides and chlorides, and firing is fired in a silica vessel to about 900 C. for about 30 the resultant mixture to about 900 C. for about 30 minutes in an atmosphere of nitrogen. The product has minutes in a neutral atmosphere.

2. The method of claim "1 wherein said gallium and copper salts are nitrates and said halide isammonium chloride.

3. The method of claim 1 wherein said metal is zinc.

4. A method of preparing a red-emitting phosphor material which comprises mixing activator quantities of gallium nitrate and copper nitrate with pure zinc sele-v nide, firing said mixture to about 900 C. for about 30 minutes in an atmosphere of nitrogen, cooling said fired product, mixing said fired product with an activator quantity of ammonium chloride, and firing said resultant mixture to about 900 C. for about '30 minutes in an atmosphere of nitrogen.

5. A method or" preparing a red-emitting phosphor material which comprising mixing about 0.01% of gallium as the nitrate-and about 0.01% copper as the nitrate with pure zinc selenide, firing said mixture to about 900 C. for about 30 minutes in .an atmosphere of nitrogen, cooling the fired product, mixing said fired product with about 2.0% of ammonium chloride, and firing the resultant mixture to about 900 C. for about 30 minutes in an atmosphere of nitrogen.

6. A phosphor material consisting essentially of the reaction product obtained by firing, to about 900 C. for about 30 minutes in a neutral atmosphere, at least one selenide selected from the class consisting of zinc selenide and cadmium selenide, with activator quantities of galham and copper salts; and then refiring, to about 900 C. for about 30 minutes in a neutral atmosphere, the resultant product with activator quantities of a halide selected from the group consisting of iodide, bromide and chlozinc selenide.

9. A phosphor material consisting essentially of the reaction product obtained by firing pure Zinc selenide.

with activator quantities of gallium nitrate and copper nitrate to about 900 C. for about 30 minutes in an atmosphere of nitrogen and then refiring the resultant product with an activator quantity of ammonium chloride to about 900 C. for about 30 minutes in an atmosphere of nitrogen.

10. A phosphor material consisting essentially of the reaction product obtained by firing pure zinc selenide with about 0.01% of gallium as the nitrate and about 0.01% of copper as the nitrate to about 900 C. for about 30 minutes in an atmosphere of nitrogen and then refin'ng the resultant product with about 2.0% of ammonium chloride to about 900 C. for about 30 minutes in an atmosphere of nitrogen.

References Cited in the file of this patent UNITED STATES PATENTS 2,623,859 Kroger Dec. 30, 1952 

6. A PHOSPHOR MATERIAL CONSISTING ESSENTIALLY OF THE REACTION PRODUCTS OBTAINED BY FIRING, TO ABOUT 900* C. FOR ABOUT 30 MINUTES IN A NEUTRAL ATMOSPHERE, AT LEAST ONE SELENIDE SELECTED FROM THE CLASS CONSISTING OF ZINC SELENIDE AND CADMIUM SELENIDE, WITH ACTIVATOR QUANTITIES OF GALLIUM AND COPPER SALTS; AND THEN REFIRING, TO ABOUT 900* C. FROM ABOUT 30 MINUTES IN A NEUTRAL ATMOSPHERE, THE RESULTAND PRODUCT WITH ACTIVATOR QUANTITIIES OF A HALIDE SELECTED FROM THE GROUP CONSISTING OF IODIDE, BROMIDE AND CHLORIDE. 